Process for ex situ sulfiding catalyst containing an S-containing additive

ABSTRACT

The present invention pertains to a process for sulfiding a catalyst composition comprising at least one hydrogenation metal component of Group VI and/or Group VIII of the Periodic Table, and an S-containing organic additive wherein the catalyst composition is contacted with hydrogen and a sulfur-containing compound in the gaseous phase, characterized in that the process is carried out ex situ. By carrying out the process ex situ, the formation of undesirable side compounds in the hydrotreating unit is prevented. Additionally, the reactor suffers less downtime, and the start-up of the reactor may be simplified. The S-containing organic additive preferably is a mercapto-compound, more preferably a mercaptocarboxylic acid represented by the general formula HS—R1-COOR, wherein R1 stands for a divalent hydrocarbon group with 1-about 10 carbon atoms and R stands for a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a linear or branched alkyl group having 1 to about 10 carbon atoms. The invention also pertains to the catalyst made by the above process and a process for hydrotreating a hydrocarbon feed by contacting the feed with the catalyst at hydrotreating conditions.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from European Patent ApplicationSerial No. 00201299.5, filed on Apr. 11, 2000 and U.S. patentapplication Ser. No. 60/201,692, filed on May 3, 2000.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to a process for ex situ sulfidinga catalyst containing an S (sulfur)-containing organic additive, inparticular a hydrotreating catalyst containing an S-containing organicadditive.

[0004] 2. Prior Art

[0005] Hydrotreating catalysts comprise hydrogenation metal components,generally a Group VI metal component such as molybdenum and/or tungstenand a Group VIII metal component, such as nickel and/or cobalt generallyon an oxidic carrier. Before use, the hydrogenation metal componentspresent in hydrotreating catalysts will generally be converted intotheir sulfides. This process is conventionally indicated as sulfidationor presulfidation. It is generally done before the catalyst is used inhydrotreating to ensure a stable reactor performance.

[0006] Hydrotreating catalysts containing S-containing organic additivesare known in the art. The addition of the S-containing organic additiveis often intended to preclude the necessity of a separate presulfidingstep.

[0007] For example, European patent application 0 300 629 and Europeanpatent application No. 0 357 295 describe hydrotreating catalystscomprising a support impregnated with at least one member of molybdenum,tungsten, and/or Group VIII of the Periodic Table, and amercapto-compound selected from mercaptocarboxylic acids,amino-substituted mercaptanes, di-mercaptanes, and thioacids. TheS-containing additive is incorporated into the catalyst composition toobviate the necessity of presulfiding, or at least make the presulfidingless difficult. In particular, the S-containing additive is incorporatedinto the catalyst to obviate the necessity of dedicating the initialpart of the reactor start-up to providing the catalyst with the amountof sulfur needed to attain equilibrium with the reaction environment, orto shorten the time necessary for doing so. Additionally, the necessityof spiking the feed with a sulfur-containing compound such as DMDS islessened or obviated. Further, since all catalyst particles alreadycontain S when they enter the unit, the homogeneity of the sulfidedproduct will be improved.

[0008] European patent application No. 0 506 206 also describes ahydrotreating catalyst comprising an S-containing additive selected fromthe group of bi-mercaptanes, aminosubstituted mercaptanes, andthiocarboxylic acids. The S-containing catalyst is again intended toavoid the necessity of presulfiding. Some of the catalysts described inthis reference are activated by a treatment with hydrogen at atemperature from room temperature up to 400° C., preferably 100-300° C.

[0009] Similar subject-matter is described in European patentapplication No. 0 338 788, and European patent application No. 0 289211.

[0010] U.S. Pat. No. 5,139,990 describes a hydrotreating catalystcomprising a carrier and hydrogenation metal components which is treatedwith an aqueous medium comprising a water-soluble or water-miscibleS-containing organic additive, followed by drying the resulting catalystand activating it with hydrogen at a temperature of 100-600° C.

[0011] U.S. Pat. No. 4,636,487 describes a hydrotreating catalystcomprising a support and a hydroxymercaptide of one or more metals,which may be the reaction product of a mercaptoalcohol and one or moremetal compounds. The catalyst may be activated with hydrogen at atemperature of 66-316° C.

[0012] European patent application No. 0 496 592 describes ahydrotreating catalyst comprising a carboxylic acid and an organicsulfur compound which may be a mercaptocarboxylic acid. The amount oforganic sulfur compound is so low that the catalyst still needs to bepresulfided. No information is given as to how this presulfidation stepshould be carried out.

[0013] EP 0 396 296 describes a catalyst preparation process in which ahydrotreating catalyst is first subjected to an ex situ presulfidingstep followed by in situ presulfiding. Ex situ presulfiding is carriedout by contacting the catalyst with a sulfur compound, e.g., byimpregnation. The in situ sulfidation may be gas phase or liquid phase,with liquid phase being preferred.

[0014] It has appeared that when the catalysts of the above referencesare brought into the hydrotreating unit, undesirable components such asacetic acid may be formed during the start-up. Additionally it was foundthat the start-up procedure is rather critical to obtain good results.

SUMMARY OF THE INVENTION

[0015] In one embodiment, our invention is a sulfidation process inwhich a catalyst composition comprising at least one hydrogenation metalcomponent of Group VI and/or Group VIII of the Periodic Table and anS-containing organic additive is contacted with hydrogen and asulfur-containing compound in the gaseous phase, the process beingcarried out ex situ.

[0016] In a second embodiment, our invention is a catalyst obtained bythe above process.

[0017] In a third embodiment, our invention is a process forhydrotreating a hydrocarbon feed by contacting the feed with the abovecatalyst at hydrotreating conditions.

[0018] Other embodiments of our invention encompass details aboutreactant compositions, process steps and conditions, etc., all of whichare hereinafter disclosed in the following discussion of each of thefacets of our invention.

DETAILED DISCRIPTION OF THE INVENTION

[0019] The Sulfidation Process

[0020] Catalysts with high activity may be obtained if the catalystcontaining an S-containing organic additive is sulfided ex situ by wayof the process of our invention. Because the process is carried outoutside the hydrotreating reactor, any undesirable side products areformed outside the hydrotreating reactor. The sulfidation unit may oftenbe better equipped to handle undesirable gases. Ex situ operation alsohas the advantage that it generates less downtime for the hydrotreatingreactor and simplifies the reactor start-up.

[0021] In the process according to our invention, the catalyst iscontacted ex situ in the gaseous phase with hydrogen and asulfur-containing compound. The sulfur-containing compound is H₂S and/ora compound which is decomposable into hydrogen sulfide under theconditions prevailing during the contacting of the catalyst withhydrogen and a sulfur-containing compound. Examples of suitablecomponents decomposable into H₂S are mercaptanes, CS₂, thiophenes,dimethyl sulfide (DMS), dimethyl disulfide (DMDS), and suitableS-containing refinery outlet gasses. The use of H₂S alone is preferred.The skilled person knows how to select a sulfur compound which willdecompose under the conditions applied.

[0022] The total amount of sulfur-containing compound which isincorporated into the catalyst in the process according to theinvention, including the amount of sulfur added by way of theS-containing additive is generally selected to correspond to about50-300%, preferably about 70-200%, more preferably about 80-150%, of thestoichiometric sulfur quantity necessary to convert the hydrogenationmetals into CO₉S₈, MoS₂, WS₂, and Ni₃S₂, respectively.

[0023] The concentration of sulfur-containing compound in the mixture ofH₂ and sulfur-containing compound is generally selected to be betweenabout 1 and about 99 wt. %, preferably between about 10 and about 80%,calculated as H₂S on the total of H₂S and hydrogen. Of course, lowersulfur concentrations in this mixture will either lengthen the durationof the process or increase the required space velocity. The applicationof gas recycle may be attractive.

[0024] The contacting in the gaseous phase with hydrogen and asulfur-containing compound can be done in one step. In that case, it ispreferably carried out at a temperature of about 150-450° C., preferablyabout 225-400° C.

[0025] However, catalysts with a higher activity may be obtained whenthe contacting in the gaseous phase with hydrogen and asulfur-containing compound is carried out in two steps, with the firststep being performed at a lower temperature than the second step. Inthis embodiment the first step is generally carried out at a temperatureof about 100-250° C., preferably about 150-225° C. The second step isgenerally carried out at a temperature of about 150-450° C., preferablyabout 200-400° C., more preferably about 225-400° C. In this two-stepembodiment, the gaseous mixtures of H₂ and sulfur-containing compoundapplied in the two steps may be the same or different. If so desired,this process may also be carried out in more than two steps, e.g., inthree steps or in a continuous mode, as long as the first step, or thestart of the process, is carried out at a lower temperature than afurther step, or later part of the process.

[0026] The total pressure during the process according to the inventionis not critical. It will generally be between atmospheric pressure andabout 10 bar.

[0027] The ex situ contacting in the gaseous phase with hydrogen and asulfur-containing compound can be carried out in any suitable manner,including in fixed bed processes and moving bed processes. Since thesulfiding step may be exothermic by nature, it is important that thetemperature of the catalyst is well-controlled. Generally, such controlis easier in a moving bed process. In the context of the presentspecification, a moving bed process is intended to encompass allprocesses in which the catalyst moves relative to the reactor. Examplesare ebullated bed processes and processes carried out in a rotaryfurnace. In the latter, the contacting can be done either co-currentlyor countercurrently, with countercurrent operation being preferred.

[0028] The amount of sulfur incorporated into the catalyst with theS-containing compound in the gas phase will generally be between about 5and about 95% of the stoichiometric sulfur quantity necessary to convertthe hydrogenation metals into Co₉S₈, MoS₂, WS₂, and Ni₃S₂, respectively.It is noted that the amount of S-containing compound with which thecatalyst is contacted in the gaseous phase will be much higher than theabove-mentioned stoichiometric amount, but not all sulfur will beincorporated into the catalyst.

[0029] It is also noted that the S-containing compound present in thegas phase does not refer to decomposition products from the S-containingadditive already present in the catalyst but refers to S-containingcompound added extraneously to the hydrogen.

[0030] It may be desirable to passivate the sulfided catalyst preparedby the process according to the invention, since sulfided catalysts maybe self-heating. Passivation can be done by contacting the sulfidedcatalyst with an oxygen-containing compound under controlled conditions.The use of an oxygen-containing gas, such as air, is a well-knownembodiment. Alternatively, the sulfided catalyst may be passivated bybeing contacted with an organic liquid, such as diesel, gas oil, whitespirit, or lube oil. Passivation processes are known in the art. See,for example, EP-897 748 and NL 8900914, which describe the use ofhydrocarbons, and V. M. Browne, S. P. A. Louwers, and R. Prins,Catalysis Today volume 10 number 3 pp 345-52 (1991) and S. P. A.Louwers, M. W. J. Craje, C. Geantet, A. M. van der Kraan, and R. Prins,Journal of Catalysis volume 144 number 2 pp. 579-96 (1993), both ofwhich describe the use of oxygen.

[0031] The Additive-containing Catalyst

[0032] In principle, the additive-containing catalyst can be anycatalyst which comprises a Group VIB hydrogenation metal and/or a GroupVIII hydrogenation metal, and an S-containing organic additive,generally on a carrier. Catalysts comprising the combination of a GroupVIB hydrogenation metal and a Group VIII hydrogenation metal arepreferred. As will be evident to the skilled person, the metals may bepresent in any form. When they are incorporated into the catalystcomposition they are often in the form of their salts or oxides. Aftercalcination they are converted partly or wholly into their respectiveoxides. After sulfidation and during use the metals are at least partlypresent in the sulfidic form.

[0033] As Group VIB metals may be mentioned molybdenum, tungsten, andchromium. Group VIII metals include nickel, cobalt, and iron. Catalystscomprising molybdenum and/or tungsten as Group VIB metal component andnickel and/or cobalt as Group VIII metal component are the most common.The catalyst usually has a metal content in the range of about 0.1 toabout 50 wt. % calculated as oxides on the dry weight of the catalystnot containing the additive. The Group VIB metal will frequently bepresent in an amount of about 5-40 wt. %, preferably about 15-30 wt. %,calculated as trioxide. The Group VIII metal will frequently be presentin an amount of about 1-10 wt. %, preferably about 2-7 wt. %, calculatedas monoxide. The catalyst may also contain other components, such asphosphorus, halogens, and boron. Particularly, the presence ofphosphorus in an amount of about 1-10 wt. %, calculated as P₂O₅, may bepreferred.

[0034] The catalyst carrier may comprise the conventional oxides, e.g.,alumina, silica, silica-alumina, alumina with silica-alumina dispersedtherein, silica-coated alumina, magnesia, zirconia, boria, and titania,as well as mixtures of these oxides. As a rule, preference is given tothe carrier comprising alumina, silica-alumina, alumina withsilica-alumina dispersed therein, or silica-coated alumina. Specialpreference is given to the carrier consisting essentially of alumina oralumina containing up to about 25 wt. % of other components, preferablysilica. A carrier comprising a transition alumina, for example an eta,theta, or gamma alumina is preferred within this group, with agamma-alumina carrier being especially preferred. Additionally, althoughat present less preferred, the catalyst may contain 0-about 60 wt. % ofzeolite.

[0035] The catalyst's pore volume (measured via N₂ adsorption) generallyis in the range of about 0.25 to about 1 ml/g. The specific surface areawill generally be in the range of about 50 to about 400 m²/g (measuredusing the BET method). Generally, the catalyst will have a median porediameter in the range of about 7-20 nm, as determined by N₂ adsorption.The figures for the pore size distribution and the surface area givenabove are determined after calcination of the catalyst at about 500° C.for one hour.

[0036] The catalyst is suitably in the form of spheres, pellets, beads,or extrudates. Examples of suitable types of extrudates have beendisclosed in the literature (see, int. al., U.S. Pat. No. 4,028,227).Highly suitable are cylindrical particles (which may be hollow or not)as well as symmetrical and asymmetrical polylobed particles (2, 3 or 4lobes).

[0037] The additive present in the catalyst may be any S-containingorganic additive. In the context of the present specification the termorganic additive refers to an additive comprising at least one carbonatom and at least one hydrogen atom.

[0038] Preferred compounds include organic compounds having at least onemercapto-group. Within the group of mercapto-compounds,mercaptocarboxylic acids represented by the general formula HS—R1-COOR,wherein R1 stands for a divalent hydrocarbon group with 1-about 10carbon atoms and R stands for a hydrogen atom, an alkali metal, analkaline earth metal, ammonium, or a linear or branched alkylgrouphaving 1 to about 10 carbon atoms. Examples include mercaptoacetic acid(HS—CH2-COOH), beta-mercaptoprioprionic acid (HS—CH2CH2-COOH),methylmercaptoacetate (HS—CH2-COOCH3), ethyl 2-mercaptoacetate(HS—CH2-COOC2H5), ethylhexyl mercaptoacetate (HS—CH2-COOC8H17), andmethyl 3-mercaptoproprionate ((HS—CH2CH2-COOCH3).

[0039] Further compounds preferred within the group ofmercapto-compounds include aminosubstituted mercaptanes represented bythe general formula H2N—R2-SH, wherein R2 stands for a divalenthydrocarbon group having 1-about 15 carbon atoms. Examples of thesecompounds include 2-amino ethanethiol (H2N—CH2CH2-SH), and 4-aminothiophenol (H2N—C6H4-SH).

[0040] Additional compounds within the group of mercapto-compounds arethe di-mercaptanes represented by the general formula HS—R3-SH, whereinR3 stands for a divalent hydrocarbon group having 1-about 15 carbonatoms. Examples of these compounds include ethanedithiol (HS—CH2CH2-SH)and 1,4-butanedithiol (HS—(CH2)4-SH).

[0041] Preferred compounds also include thioacids of the formulaR4-COSH, wherein R4 stands for a monovalent hydrocarbon group having1-about 15 carbon atoms. Examples of these compounds include thioaceticacid (CH3-COSH) and thiobenzoic acid (C6H5COSH). Dithioacids of theformula HSOC—R5-COSH, wherein R5 is a divalent hydrocarbon group with1-about 15 carbon atoms may also be suitable. An example is dithioadipicacid (HSOC—C4H10-COSH).

[0042] Preferred compounds also include mercaptoalcohols of the generalformula R6S—R5-(OH)n, wherein R5 represents an alkyl group having from 1to 15 carbon atoms or a phenyl group, R6 represents a hydrogen atom oran alkyl group having 1 or 2 carbon atoms, and n is 1 or 2. Examples ofthese compounds include 2-mercaptoethanol, 2-(methylthio)ethanol,2-(ethylthio)ethanol, 3-mercapto-2-butanol, 4-mercaptophenol,2-(methylthio)phenol, 4-(methylthio)phenol, 2-(ethylthio)phenol,3-mercapto-1,2,-propanediol, 3-methylthio-1,2, propanediol, and3-ethylthio-1,2, propanediol.

[0043] Other suitable compounds include sulphoxides of the formulaR7-SO—R8, wherein R7 and R8 are hydrocarbon groups with 1-5 carbonatoms. An example is dimethyl sulfoxide (CH3-SO—CH3).

[0044] Ammonium thiocyanate and thiourea may also be useful compounds,as may be the various dithiocarbamic acids and the salts thereof, suchas ethylene bisdithiocarbamic acid and its salts, and dimethyldithiocarbamic acid and its salts. Other suitable compounds includemercaptodiathiazoles and their salts, such as2,5-dimercapto-1,3,4,-diathiazoles and its salts.

[0045] Other compounds which may be useful are polysulfides of theformula R9-Sx—R10, wherein x is a value of 1-about 15 and R9 and R10 arealkyl groups, preferably branched alkyl groups, with 1-about 30 carbonatoms. Related compounds are those with the formula HO—R11-Sx—R12-OH,wherein x is a value of 1-15 and R11 and R12 are alkyl groups with1-about 8 carbon atoms.

[0046] At this point in time the mercapto-containing compounds, inparticular the mercaptocarboxylic acids are considered preferred forreasons of catalyst activity. Other compounds, in particularly thosewhich are soluble in or miscible with water may be preferred forenvironmental reasons (less smell and no organic solvent necessary).

[0047] A single compound as well as a combination of compounds may beused as additive.

[0048] The amount of additive present in the additive-containingcatalyst depends on the specific situation. It was found that theappropriate amount of additive generally lies in the range of about0.01-2.5 moles of additive per mole of hydrogenation metals present inthe catalyst. If the amount of additive added is too low, theadvantageous effect associated with its presence will not be obtained.On the other hand, the presence of an exceptionally large amount ofadditive will not improve its effect. Generally it is intended that theamount of sulfur incorporated into the catalyst by way of the additiveis selected to correspond to about 5-200%, preferably about 50-200%,more preferably about 80-150%, of the stoichiometric sulfur quantitynecessary to convert the hydrogenation metals into Co₉S₈, MoS₂, WS₂, andNi₃S₂, respectively.

[0049] The way in which the additive is incorporated into the catalystcomposition is not critical to the process according to the invention.The additive may be incorporated into the catalyst composition prior to,subsequent to, or simultaneously with the incorporation of thehydrogenation metal components.

[0050] For example, the additive can be incorporated into the catalystcomposition prior to the hydrogenation metal components by being addedto the carrier before the hydrogenation metal components are. This canbe done by mixing the additive with the carrier material before it isshaped, or by impregnating the shaped carrier material with theadditive. This embodiment is not preferred at this point in time.

[0051] Alternatively, the additive can be incorporated into the catalystcomposition simultaneously with the hydrogenation metal components. Thiscan be done, e.g., by mixing the additive and the hydrogenation metalcomponents with the carrier material before shaping or by impregnatingthe carrier with an impregnation solution comprising the hydrogenationmetal components and the additive, followed by drying under suchconditions that at least part of the additive is maintained in thecatalyst.

[0052] It is also possible to incorporate the additive into the catalystcomposition subsequent to the hydrogenation metal components. This canbe done, e.g., by first incorporating the hydrogenation metal componentsinto the catalyst composition, e.g., by mixing them with the carriermaterial or by impregnating the carrier with them, optionally followedby drying and/or calcining, and subsequently incorporating the additive,e.g., by impregnation, optionally followed by drying under suchconditions that at least part of the additive is maintained in thecatalyst.

[0053] Depending on the nature of the additive and the way in which itis incorporated into the catalyst composition, the additive may be usedin solid form, in liquid form, or dissolved in a suitable solvent. Itmay be preferred for the additive to be incorporated into the catalystdissolved in water.

[0054] Use of the Sulfided Catalyst Prepared According to the Invention

[0055] The catalyst sulfided by the process according to the inventioncan be used in the hydrotreating of hydrocarbon feeds. The hydrotreatinggenerally takes place under conventional hydrotreating conditions, suchas temperatures in the range of about 250-450° C., pressures in therange of about 5-250 bar, space velocities in the range of about0,1-h⁻¹, and H₂/oil ratios in the range of about 50-2000 Nl/l. Examplesof suitable feeds include middle distillates, kerosine, naphtha, vacuumgas oils, heavy gas oils and residues. Preferably, the hydrocarbon feedcontains at least about 0.2 wt % of sulfur, calculated as atomic sulfurS. Examples of suitable hydrotreating reactions are (deep)hydrodesulfurisation, hydrodenitrogenation, hydrodearomatisation, andhydrodemetallisation. (Deep) hydrodesulfurisation, hydrodenitrogenation,and hydrodearomatisation are preferred.

EXAMPLE

[0056] A conventional hydrotreating catalyst containing 24 wt. %molybdenum, calculated as trioxide, 4 wt. % nickel, calculated as oxide,and 7 wt. % phosphorus, calculated as P₂O₅, on a gamma-alumina carrierwas impregnated by pore volume impregnation with a solution ofHS—CH₂—COOH in water, containing 1 mole HS—CH₂—COOH per mole of thetotal of molybdenum and nickel. Then, the catalyst was dried rotating inhot air to a product temperature of about 100° C.

[0057] The additive-containing starting catalyst (10 ml) was sulfided inthe gas phase at atmospheric pressure using a mixture of 10 vol. % H₂Sin H₂ (flow=5 l/hr) in one step. The temperature was increased by 0.5°C. per minute to 300° C. and held at that temperature for 3 hours.

[0058] The catalyst was tested in an upflow tubular reactor using a SRGOwith the properties given in table 1. The reaction conditions are givenin table 2. TABLE 1 feedstock properties Type feed Straight run gas oilNitrogen (ASTM D-4629) 115 (ppmwt) Sulfur (ASTM D-4294) (wt. %) 1.2Density 15° C. (g/ml) 0.84 Dist. (° C.) (ASTM D 1160) IBP 5 vol. % 17710 vol. % 203 30 vol. % 254 50 vol. % 292 70 vol. % 330 90 vol. % 386 95vol. % 412 FBP 476

[0059] TABLE 2 Reaction conditions Temperature (° C.) 340 Pressure (bar)30 H₂/oil (Nl/l) 125 LHSV (h-I) 2.0

[0060] The oil product from the reactor was analysed. The results aregiven in Table 3 below. TABLE 3 test results feed product S  1.2 wt. % 0.066 wt. % N 115 ppm 28 ppm

1. A process for sulfiding a catalyst composition comprising at leastone hydrogenation metal component of Group VI and/or Group VIII of thePeriodic Table, and an S-containing organic additive, wherein thecatalyst composition is contacted with hydrogen and a sulfur-containingcompound in the gaseous phase, the process being carried out ex situ. 2.The process of claim 1 wherein the ex situ sulfided catalyst ispassivated after the treatment with hydrogen and the sulfur-containingcompound.
 3. The process of claim 1 wherein the sulfur-containingcompound applied in the gaseous phase is H₂S.
 4. The process of claim 1wherein the S-containing organic additive comprises at least one carbonatom and at least one hydrogen atom.
 5. The process of claim 1 whereinthe S-containing organic additive is an organic compound comprising amercapto-group.
 6. The process of claim 5 wherein the S-containingorganic additive is a mercapto acid represented by the general formulaHS—R1-COOR, wherein R1 stands for a divalent hydrocarbon group with1-about 10 carbon atoms and R stands for a hydrogen atom, an alkalimetal, an alkaline earth metal, ammonium, or a linear or branched alkylgroup having 1 to about 10 carbon atoms.
 7. The process of claim 1wherein the S-containing organic additive comprises about 0.01-2.5 molesof additive per mole of hydrogenation metals present in the catalyst. 8.The process of claim 1 wherein the catalyst has a metal content in therange of about 0.1 to about 50 wt. % calculated as oxides on the dryweight of the catalyst not containing the S-containing organic additive.9. The process of claim 1 wherein the Group VIB metal is present in anamount of about 5-40 wt. %, calculated as trioxide.
 10. The process ofclaim 1 wherein the Group VIII metal is present in an amount of about1-10 wt. %, calculated as monoxide.
 11. The process of claim 1 whereinthe group VI metals are selected from Mo and/or W and the group VIIImetals are selected from Co and/or Ni.
 12. The process of claim 11wherein the amount of sulfur incorporated into the catalyst by way ofthe S-containing organic additive is selected to correspond to about5-200% of the stoichiometric sulfur quantity necessary to convert thehydrogenation metals into Co₉S₈, MoS₂, WS₂, and/or Ni₃S₂, respectively.13. The process of claim 1 wherein the contacting of the catalyst withhydrogen and a sulfur-containing compound takes place in one step at atemperature of about 150-450° C.
 14. The process of claim 1 wherein thecontacting of the catalyst with hydrogen and a sulfur-containingcompound is carried out in two steps, with the first step beingperformed at a temperature which is lower than that of the second step.15. The process of claim 14 wherein the first step is carried out at atemperature of about 100-250° C. and the second step is carried out at atemperature of about 150-450° C.
 16. A catalyst obtained by the processof claim
 1. 17. A process for the hydrotreating of hydrocarbon feedswherein the hydrocarbon feeds are contacted with the catalyst obtainedby the process of claim 1 at hydrotreating conditions.
 18. The processof claim 17 wherein said hydrotreating conditions comprise a temperaturein the range of about 250-450° C., a pressure in the range of about5-250 bar, a space velocity in the range of about 0,1-10 h⁻¹ and anH₂/oil ratio in the range of about 50-2000 Nl/l.